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At least 73 records · Page 4

Isothermal dendritic growth - A proposed microgravity experiment

This paper describes an isothermal dendritic growth experiment (IDGE), a microgravity-oriented spaceborne scientific experiment designed to obtain 'convection-free' dendritic growth and thereby provide a test of dendritic growth theory. The apparatus includes a controlled thermostatic bath capable of providing + or - 2 mK stability, a photographic data collection system, a crystal growth chamber ensuring 'free' dendritic growth, and an optical RAM camera for crystal growth detection. The experiment will be carried on essentially automatically aboard the Materials Science Laboratory in the cargo bay of the Space Shuttle. The results of preliminary ground-based studies are presented.

Glicksman, M. E.↗

Thermosolutal convection and macrosegregation in dendritic alloys

A mathematical model of solidification, that simulates the formation of channel segregates or freckles, is presented. The model simulates the entire solidification process, starting with the initial melt to the solidified cast, and the resulting segregation is predicted. Emphasis is given to the initial transient, when the dendritic zone begins to develop and the conditions for the possible nucleation of channels are established. The mechanisms that lead to the creation and eventual growth or termination of channels are explained in detail and illustrated by several numerical examples. A finite element model is used for the simulations. It uses a single system of equations to deal with the all-liquid region, the dendritic region, and the all-solid region. The dendritic region is treated as an anisotropic porous medium. The algorithm uses the bilinear isoparametric element, with a penalty function approximation and a Petrov-Galerkin formulation. The major task was to develop the solidification model. In addition, other tasks that were performed in conjunction with the modeling of dendritic solidification are briefly described.

Poirier, David R.↗

Dendrite preventing separator for secondary lithium batteries

Dendrites are prevented from shorting a secondary lithium battery by use of a first porous separator, such as porous polypropylene, adjacent to the lithium anode that is unreactive with lithium and a second porous fluoropolymer separator between the cathode and the first separator, such as polytetrafluoroethylene, that is reactive with lithium. As the tip of a lithium dendrite contacts the second separator, an exothermic reaction occurs locally between the lithium dendrite and the fluoropolymer separator. This results in the prevention of the dendrite propagation to the cathode.

Shen, David H.↗

Space flight data from the isothermal dendritic growth experiment

The Isothermal Dendritic Growth Experiment (IDGE) is a NASA space flight experiment which flew as part of the United States Microgravity Payload (USMP-2), in early 1994. The IDGE measured dendritic growth rates, tip radii, and crystal morphologies of ultra-pure succinonitrile (CN-(CH2)2-CN) at supercoolings in the range from 0.05 - 2.0 K. Data taken in the form of slow-scan binary digitized images telemetered to the ground from orbit in near-real time, combined with the IDGE terrestrial data set, provide the first quantitative assessment of various theories on dendritic solidification and the effects of convection on dendritic growth.

Glicksman, M. E.↗

Dendrite preventing separator for secondary lithium batteries

Dendrites are prevented from shorting a secondary lithium battery by use of a first porous separator such as porous polypropylene adjacent the lithium anode that is unreactive with lithium and a second porous fluoropolymer separator between the cathode and the first separator such as polytetrafluoroethylene that is reactive with lithium. As the tip of a lithium dendrite contacts the second separator, an exothermic reaction occurs locally between the lithium dendrite and the fluoropolymer separator. This results in the prevention of the dendrite propagation to the cathode.

Shen, David H.↗

Macrosegregation During Dendritic Arrayed Growth of Hypoeutectic Pb-Sn Alloys: Influence of Primary Arm Spacing and Mushy Zone Length

Thermosolutal convection in the dendritic mushy zone occurs during directional solidification of hypoeutectic lead tin alloys in a positive thermal gradient, with the melt on the top and the solid below. This results in macrosegregation along the length of the solidified samples. The extent of macrosegregation increases with increasing primary dendrite spacings for constant mushy zone length. For constant primary spacings, the macrosegregation increases with decreasing mushy zone length. Presence of convection reduces the primary dendrite spacings. However, convection in the interdendritic melt has significantly more influence on the spacings as compared with that in the overlying melt, which is caused by the solutal buildup at the dendrite tips.

Tewari, S. N.↗

The Transient Dendritic Solidification Experiment (TDSE)

Dendritic solidification is a common mode of solidification. It is also an important model problem in nonequilibrium physics and pattern formation physics. Current theories couple the transfer of latent heat with selection mechanisms at the interface. Measurements of succinonitrile (SCN) dendrites in microgravity show reasonable agreement between heat transfer predictions and experiment. However, data and analysis for assessing interfacial physics theories are less definitive. We are studying, and will present data on, transient effects in dendritic growth of SCN. We employ the Clapeyron pressure/melting temperature effect to make a rapid change in a sample's hydrostatic pressure, and thereby rapidly change the specimen's melting temperature, forcing the dendrite to select a new steady-state. These initial measurements show some surprising and non-intuitive effects.

Koss, M. B.↗

Convection Effects in Three-dimensional Dendritic Growth

A phase-field model is developed to simulate free dendritic growth coupled with fluid flow for a pure material in three dimensions. The preliminary results presented here illustrate the strong influence of convection on the three-dimensional (3D) dendrite growth morphology. The detailed knowledge of the flow and temperature fields in the melt around the dendrite from the simulations allows for a detailed understanding of the convection effects on dendritic growth.

Lu, Yili↗

Disruption of an Aligned Dendritic Network by Bubbles During Re-Melting in a Microgravity Environment

The quiescent Microgravity environment can be quite dynamic. Thermocapillary flow about "large" static bubbles on the order of 1mm in diameter was easily observed by following smaller tracer bubbles. The bubble induced flow was seen to disrupt a large dendritic array, effectively distributing free branches about the solid-liquid interface. "Small" dynamic bubbles were observed to travel at fast velocities through the mushy zone with the implication of bringing/detaching/redistributing dendrite arm fragments at the solid-liquid interface. Large and small bubbles effectively re-orient/re-distribute dendrite branches/arms/fragments at the solid liquid interface. Subsequent initiation of controlled directional solidification results in growth of dendrites having random orientations which significantly compromises the desired science.

Grugel, Richard N.↗

Primary Dendrite Array Morphology: Observations from Ground-based and Space Station Processed Samples

Influence of natural convection on primary dendrite array morphology during directional solidification is being investigated under a collaborative European Space Agency-NASA joint research program, "Microstructure Formation in Castings of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions (MICAST)". Two Aluminum-7 wt pct Silicon alloy samples, MICAST6 and MICAST7, were directionally solidified in microgravity on the International Space Station. Terrestrially grown dendritic monocrystal cylindrical samples were remelted and directionally solidified at 18 K/cm (MICAST6) and 28 K/cm (MICAST7). Directional solidification involved a growth speed step increase (MICAST6-from 5 to 50 micron/s) and a speed decrease (MICAST7-from 20 to 10 micron/s). Distribution and morphology of primary dendrites is currently being characterized in these samples, and also in samples solidified on earth under nominally similar thermal gradients and growth speeds. Primary dendrite spacing and trunk diameter measurements from this investigation will be presented.

Tewari, Surendra↗

Primary Dendrite Array: Observations from Ground-Based and Space Station Processed Samples

Influence of natural convection on primary dendrite array morphology during directional solidification is being investigated under a collaborative European Space Agency-NASA joint research program, Microstructure Formation in Castings of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions (MICAST). Two Aluminum-7 wt pct Silicon alloy samples, MICAST6 and MICAST7, were directionally solidified in microgravity on the International Space Station. Terrestrially grown dendritic monocrystal cylindrical samples were remelted and directionally solidified at 18 K per centimeter (MICAST6) and 28 K per centimeter (MICAST7). Directional solidification involved a growth speed step increase (MICAST6-from 5 to 50 millimeters per second) and a speed decrease (MICAST7-from 20 to 10 millimeters per second). Distribution and morphology of primary dendrites is currently being characterized in these samples, and also in samples solidified on earth under nominally similar thermal gradients and growth speeds. Primary dendrite spacing and trunk diameter measurements from this investigation will be presented.

Tewari, Surendra N.↗

Dendritic gold nanoparticles and methods of synthesis

A method of producing dendritic gold nanoparticles by combining a gold precursor solution, a reducing agent, and a bifunctional peptide having an amine-rich amino acid sequence into a buffered aqueous solution in a single container, and agitating the mixture causing the formation of the dendritic gold nanoparticles having a surface with a positive charge and a second end portion of the bifunctional peptide exposed on the surface of the dendritic gold nanoparticles. The dendritic gold nanoparticles may be used to deliver therapeutic, diagnostic, and/or immunogenic amino acid sequences as portions of the bifunctional peptide.

Mao, Chuanbin↗

Precise Tailoring of Lithium-Ion Transport for Ultralong-Cycling Dendrite-Free All-Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries can address crucial challenges regarding insufficient battery cycling life and energy density. The demonstration of long-cycling dendrite-free all-solid-state lithium metal batteries requires precise tailoring of lithium-ion transport of solid-state electrolytes (SSEs). Here, in this work, a proof of concept is reported for precise tailoring of lithium-ion transport of a halide SSE, Li 3 InCl 6 , including intragranular (within grains) but also intergranular (between grains) lithium-ion transport. Lithium-ion migration tailoring mechanism in crystals is developed by unexpected enhanced Li, In, and Cl vacancy populations and lower energy barrier for hopping. The lithium-ion transport tailoring mechanism between the grains is determined by the elimination of voids between grains and the formation of unexpected supersonic conducting grain boundaries, boosting the lithium dendrite suppression ability of SSE. Due to boosted lithium-ion conduction and dendrite-suppression ability, the all-solid-state lithium metal batteries coupled with Ni-rich LiNi 0.83 Co 0.12 Mn 0.05 O 2 cathodes and lithium metal anodes demonstrate breakthroughs in electrochemical performance by achieving extremely long cycling life at a high current density of 0.5 C (2000 cycles, 93.7% capacity retention). This concept of precise tailoring of lithium-ion transport provides a cost, time, and energy efficient solution to conquer the remaining challenges in all-solid-state lithium-metal batteries for fast developing electric vehicle markets.

25 ENERGY STORAGE↗

Stress engineering for crack and dendrite prevention in solid electrolytes via ion implantation

Solid-state batteries represent a promising technology that offers safer and more densely packed energy storage. A primary cause of failure in solid-state cells is the penetration of metal dendrites through the solid electrolyte. Here, we report that fluorine-ion implantation can enhance the mechanical resistance of solid electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 to dendrite propagation by inducing residual compressive stress in the subsurface of the electrolyte. Ion implantation modifies subsurface residual stress and also alters the electrolyte’s surface, resulting in multifunctional enhancement. The combined chemical and mechanical effects of ion implantation enable reversible lithium metal stripping and plating at elevated current densities while enhancing air stability and mitigating the formation of a harmful carbonate layer at the surface. This study provides new insights into a scalable dendrite-suppression strategy for designing solid-state batteries suitable for cycling at room temperature and low stack pressures.

25 ENERGY STORAGE↗

Can a Coating Mitigate Molten Na Dendrite Growth in NaSICON Under High Current Density?

Alkali metals are among the most desirable negative electrodes for long duration energy storage due to their extremely high capacities. Currently, only high-temperature (>250 °C) batteries have successfully used alkali electrodes in commercial applications, due to limitations imposed by solid electrolytes, such as low conductivity at moderate temperatures and susceptibility to dendrites. Toward enabling the next generation of grid-scale, long duration batteries, we aim to develop molten sodium (Na) systems that operate with commercially attractive performance metrics including high current density (>100 mA cm –2 ), low temperature (<200 °C), and long discharge times (>12 h). In this work, we focus on the performance of NaSICON solid electrolytes in sodium symmetric cells at 110 °C. Specifically, we use a tin (Sn) coating on NaSICON to reduce interfacial resistance by a factor of 10, enabling molten Na symmetric cell operation with “discharge” durations up to 23 h at 100 mA cm –2 and 110 °C. Unidirectional galvanostatic testing shows a 70% overpotential reduction, and electrochemical impedance spectroscopy (EIS) highlights the reduction in interfacial resistance due to the Sn coating. Detailed scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) show that Sn-coated NaSICON enables current densities of up to 500 mA cm –2 at 110 °C by suppressing dendrite formation at the plating interface (Mode I). In conclusion, this analysis also provides a mechanistic understanding of dendrite formation at current densities up to 1000 mA cm –2 , highlighting the importance of effective coatings that will enable advanced battery technologies for long-term energy storage.

25 ENERGY STORAGE↗

Operando Optical Microscopy for Visualization of Dendrite Growth in an Argyrodite LPSCl–Polymer Composite Electrolyte

Herein, we demonstrate the utility of optical microscopy as an accessible technique for the in situ visualization of dendrite growth within polymer–sulfide composite solid-state electrolytes. The composite electrolyte features in situ polymerization and cross-linking of the polymer between ceramic particles, which opens up extensive opportunities for accelerated materials discovery, given the vast array of acrylate/methacrylate monomers available. Specifically, the cross-linked polymer poly(triethylene glycol dimethacrylate) (poly(TEGDMA)) was observed to effectively fill pores and inhibit dendrite growth at the lithium metal interface, attributed to its glassy state at room temperature. This work represents the first application of optical microscopy to illustrate that the incorporation of glassy, undoped polymers such as poly(TEGDMA) can serve as a viable strategy for dendrite suppression in solid-state composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dual-cation electrolytes

Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.

25 ENERGY STORAGE↗

Electrodeposited Sn–Cu@Sn dendrites for selective electrochemical CO 2 reduction to formic acid

Large-scale CO 2 electrolysis can be applied to store renewable energy in chemicals. Recent developments in gas diffusion electrodes now enable a commercially relevant current density. However, the low selectivity of the CO 2 reduction reaction (CO 2 RR) still hinders practical applications. The selectivity of the CO 2 RR highly depends on the electrocatalyst. Sn catalysts are considered promising cathode materials for the production of formic acid. The selectivity of Sn catalysts can be regulated by controlling their morphology or alloying them with secondary metals. In this work, we enhanced the selectivity of CO 2 reduction to formic acid by synthesizing Sn–Cu@Sn dendrites that have a core@shell architecture. The Sn–Cu@Sn dendrites were prepared by a scalable electro-deposition method. The electronic structure was modified to suppress a reaction pathway for CO production on the Sn surface. Notably, the Sn shell inhibited the cathodic corrosion of Cu during the CO 2 RR. On a gas diffusion electrode, the Sn–Cu@Sn dendrites exhibited 84.2% faraday efficiency to formic acid for 120 h with high stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗